WO2011049100A1 - Plaque de verre pour substrat, son procédé de production, et procédé de production d'un panneau tft - Google Patents

Plaque de verre pour substrat, son procédé de production, et procédé de production d'un panneau tft Download PDF

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Publication number
WO2011049100A1
WO2011049100A1 PCT/JP2010/068410 JP2010068410W WO2011049100A1 WO 2011049100 A1 WO2011049100 A1 WO 2011049100A1 JP 2010068410 W JP2010068410 W JP 2010068410W WO 2011049100 A1 WO2011049100 A1 WO 2011049100A1
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WO
WIPO (PCT)
Prior art keywords
glass plate
glass
substrate
temperature
sio
Prior art date
Application number
PCT/JP2010/068410
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English (en)
Japanese (ja)
Inventor
知之 辻村
有一 黒木
学 西沢
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN201080043823.2A priority Critical patent/CN102574725B/zh
Priority to EP10824949.1A priority patent/EP2492246A4/fr
Priority to JP2011537269A priority patent/JP5761025B2/ja
Publication of WO2011049100A1 publication Critical patent/WO2011049100A1/fr
Priority to US13/435,222 priority patent/US8791036B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates

Definitions

  • an alkali-free glass containing no alkali metal oxide has been used for a glass substrate for an LCD panel.
  • the reason for this is that if an alkali metal oxide is contained in the glass substrate, the thin film transistor (TFT) used by the alkali ions in the glass substrate to drive the LCD panel during the heat treatment performed in the LCD panel manufacturing process. This is because it may diffuse into the semiconductor film and cause deterioration of TFT characteristics.
  • alkali-free glass has a low coefficient of thermal expansion and a high glass transition point (Tg), so there is little dimensional change in the LCD panel manufacturing process, and there is little effect on display quality due to thermal stress when using the LCD panel. Therefore, it is preferable as a glass substrate for an LCD panel.
  • the present inventor has found that the glass compaction (heat shrinkage rate) can greatly affect the film forming quality (film forming pattern accuracy) on the glass substrate in the heat treatment in the low temperature range described above.
  • the glass compaction heat shrinkage rate
  • it must be manufactured under conditions where the amount of water in the glass is high (for example, fuel such as city gas and heavy oil is burned by an oxygen combustion method or an oxygen and air combustion method).
  • fuel such as city gas and heavy oil is burned by an oxygen combustion method or an oxygen and air combustion method.
  • a hydroxide as a glass raw material
  • the ⁇ -OH value (mm ⁇ 1 ) of the glass is used as an indicator of the moisture content in the glass.
  • the productivity improvement is, for example, efficient dissolution by selecting a combustion method
  • the quality improvement is, for example, improvement of defoaming property by decompression defoaming.
  • the present invention contains an alkali metal oxide, has a small amount of B 2 O 3, and has a water content of 0.05 to 0 in terms of ⁇ -OH value (mm ⁇ 1 ). .5, and compaction during heat treatment at a low temperature (150 to 300 ° C.) in the TFT panel manufacturing process (specifically, heat treatment in the step of forming a gate insulating film) is small, particularly large (for example, one side is It is an object of the present invention to provide a glass plate for a substrate which can be suitably used as a glass substrate for a TFT panel having a size of 2 m or more, a method for producing the same, and a method for producing a TFT panel using the glass plate.
  • the above-mentioned compaction is small. It aims at providing the manufacturing method of a TFT panel using the board, its manufacturing method, and the said glass plate.
  • the glass plate for a substrate of the present invention is a glass suitable for lowering the temperature of the heat treatment process of the TFT process, that is, when being heat-treated at 150 to 300 ° C., and is effective for energy saving of the TFT process.
  • the glass plate for a substrate of the present invention is suitable as a glass substrate for a TFT panel, but can be used for other display substrates such as a plasma display panel (PDP) and an inorganic electroluminescence display.
  • PDP plasma display panel
  • an inorganic electroluminescence display For example, when used as a glass plate for PDP, it has a smaller coefficient of thermal expansion than that of a conventional glass plate for PDP, so that it is possible to suppress glass breakage in the heat treatment step.
  • the glass plate for substrates of this invention can be used also for uses other than a display panel. For example, it can also be used as a glass plate for a solar cell substrate.
  • the glass plate for substrates of the present invention is expressed in mol% on the basis of oxide, and as a glass mother composition, SiO 2 67-72, Al 2 O 3 1-7, B 2 O 3 0-4, MgO 11-15, CaO 0-3, SrO 0-3, BaO 0-2, ZrO 2 0-4, Na 2 O 8-15, K 2 O 0-7, Consists of SiO 2 + Al 2 O 3 is 73 to 77, MgO + CaO + SrO + BaO is 11 to 17, Na 2 O + K 2 O is 8 to 17, K 2 O / (Na 2 O + K 2 O) ⁇ 0.13 ⁇ (SiO 2 + Al 2 O 3 ) ⁇ 9.4 is satisfied, ⁇ -OH value (mm ⁇ 1 ) is 0.05 to 0.5, The thermal shrinkage rate (C) is 16 ppm or less.
  • the glass plate for a substrate of the present invention preferably has a ⁇ -OH
  • Compaction is the glass heat shrinkage generated by relaxation of the glass structure during the heat treatment.
  • the heat shrinkage rate (C) means that the glass plate is heated to the transition temperature Tg + 50 ° C., held for 1 minute, cooled to room temperature at 50 ° C./min, and then the surface of the glass plate
  • the compaction (C) will be described more specifically.
  • the compaction (C) means a value measured by the method described below. First, after a target glass plate is melted at 1600 ° C., the molten glass is poured out, cooled into a plate shape, and then cooled. The obtained glass plate is polished to obtain a sample of 200 mm ⁇ 20 mm ⁇ 2.8 mm. Next, the obtained glass plate is heated to a transition temperature Tg + 50 ° C., held at this temperature for 1 minute, and then cooled to room temperature at a temperature lowering rate of 50 ° C./min.
  • SiO 2 A component that forms a glass skeleton. If it is less than 67 mol% (hereinafter simply referred to as “%”), the heat resistance and chemical durability of the glass are lowered, and the thermal expansion coefficient may be increased. In addition, when the fluctuation of the compaction (C) with respect to the ⁇ -OH value of the glass becomes large and the ⁇ -OH value (mm ⁇ 1 ) is 0.2 to 0.5, the compaction (C) should be 16 ppm or less. May become difficult.
  • the content of SiO 2 is preferably 67 to 71%, more preferably 68 to 71%, and further preferably 69 to 71%.
  • Al 2 O 3 Raises glass transition point, improves heat resistance and chemical durability, and raises Young's modulus. If the content is less than 1%, the glass transition point is lowered. In addition, when the fluctuation of the compaction (C) with respect to the ⁇ -OH value of the glass becomes large and the ⁇ -OH value (mm ⁇ 1 ) is 0.2 to 0.5, the compaction (C) should be 16 ppm or less. May become difficult. However, if it exceeds 7%, the high-temperature viscosity of the glass increases, and the meltability may deteriorate. Further, the devitrification temperature is increased, and the moldability may be deteriorated.
  • the content of Al 2 O 3 is preferably 2 to 6%, more preferably 3 to 5%.
  • SiO 2 and Al 2 O 3 are glass network-forming components, and if the total content is less than 73%, the heat resistance and chemical durability of the glass may decrease, and the thermal expansion coefficient may increase. is there.
  • the compaction (C) should be 16 ppm or less. May become difficult.
  • the total content of SiO 2 and Al 2 O 3 is preferably 73 to 76%, more preferably 73.5 to 76%.
  • the total content of SiO 2 and Al 2 O 3 is preferably 73 to 77%, more preferably 73 to 76%. Preferably, it is 73.5 to 76%.
  • B 2 O 3 The glass plate for a substrate of the present invention has a B 2 O 3 content as low as 4% or less. Therefore, when glass is melted during glass plate production, there is little volatilization of B 2 O 3 in the melting step, clarification step and molding step, especially in the melting step and clarification step, and the glass substrate to be produced is homogeneous. Excellent flatness. As a result, when used as a glass plate for a TFT panel that requires a high degree of flatness, the polishing amount of the glass plate can be reduced as compared with a conventional glass plate for a substrate. Moreover, even when considering the environmental burden by volatilization of B 2 O 3, the content of B 2 O 3 is that less is preferable.
  • SrO It can be contained because it has the effect of lowering the viscosity at the time of melting the glass and promoting the melting. However, if it exceeds 3%, the thermal expansion coefficient and compaction (C) of the glass plate may increase.
  • the content of SrO is preferably 0 to 1%, more preferably 0 to 0.5%, and still more preferably substantially not contained.
  • BaO Since it has the effect of decreasing the viscosity at the time of melting of glass and promoting melting, it can be contained. However, if it exceeds 2%, the thermal expansion coefficient and compaction (C) of the glass plate may be increased.
  • the content of BaO is preferably 0 to 1%, more preferably 0 to 0.5%, and still more preferably substantially not contained. In the case of a composition that takes into account the influence of B 2 O 3 and BaO described later, if the BaO content exceeds 4%, the thermal expansion coefficient and compaction (C) of the glass plate may be increased.
  • the content of BaO is preferably 0 to 2%, more preferably 0 to 1%, and more preferably 0 to 0.5%. More preferably, it does not contain substantially.
  • Na 2 O and K 2 O In order to sufficiently lower the viscosity at the glass melting temperature, the total amount of Na 2 O and K 2 O is 8% or more. However, if the total amount exceeds 17%, the thermal expansion coefficient may increase.
  • the total content of Na 2 O and K 2 O is preferably 9 to 16%, more preferably 9.5 to 14%, and even more preferably 10 to 13.5%.
  • ZrO 2 At the time of glass production, it has the effect of improving the clarity of glass, so it can be contained up to 4%. However, if it exceeds 4%, the density increases. In consideration of reduction of glass compaction (C), 2% or less is preferable.
  • the content of ZrO 2 is preferably 2 to 4%, more preferably 2.5 to 4%, and further preferably 3 to 4%.
  • the glass plate for a substrate of the present invention preferably has a composition satisfying the following formula (1) in addition to the above-described contents of the individual components in the mother composition.
  • the inventor manufactured glass under the condition that the ⁇ -OH value (mm ⁇ 1 ) is 0.2 or more while changing individual components in the glass matrix composition, and examined the compaction of the glass.
  • FIG. 1 shows the ratio of K 2 O to the alkali metal oxide in the glass (K 2 O / Na 2 O + K 2 O) and the compaction of the glass (G 2 O) for glasses having different amounts of SiO 2 and Al 2 O 3.
  • B 2 O 3 has a coordination number of 3 and is smaller than the coordination number 4 of SiO 2 and Al 2 O 3 , the contribution ratio of B 2 O 3 is lower than these.
  • the contribution of B 2 O 3 was 0.5.
  • BaO is a component whose ionic radius is large and difficult to move as compared with other alkaline earth metal oxides such as MaO, CaO, and SrO, and therefore, it is considered that BaO contributes less to structural relaxation during heat treatment.
  • the contribution of BaO was set to 0.3.
  • even the composition satisfying the above formula (2) preferably satisfies the above formula (1).
  • the glass plate for substrates of the present invention has a compaction (C) of 16 ppm or less. Moreover, Preferably it is 10 ppm or less, More preferably, it is 8 ppm or less. Moreover, although it is suitable as a glass substrate for TFT panels, it can be used for other display substrates such as a plasma display panel (PDP) and an inorganic electroluminescence display. It can also be used for applications other than display panels. For example, it can also be used as a glass plate for a solar cell substrate.
  • C compaction
  • the manufacturing method of the glass plate for substrates of this invention is demonstrated.
  • the dissolution / clarification step and the molding step are performed in the same manner as when manufacturing a conventional glass plate for substrates.
  • the glass plate for substrates of the present invention is an alkali glass substrate containing an alkali metal oxide (Na 2 O, K 2 O), SO 3 can be effectively used as a fining agent, and a molding method Suitable for the float process.
  • a float method capable of forming a large area glass plate easily and stably with the recent increase in size of liquid crystal televisions and the like is used. Is preferred.
  • the glass of the comparative examples (Examples 25 to 29) has a large compaction (C) of 17 ppm or more, there is a possibility of affecting the thermal shrinkage at a low temperature in the TFT panel manufacturing process.
  • the substrate glass plate of the present invention having a compaction (C) of 16 ppm or less is obtained.
  • the glass melting step of the present invention when SO 3 is used as a fining agent, a glass with excellent fining effect and few bubbles can be obtained.
  • the glass plate for substrates of the present invention can be suitably used particularly as a glass substrate for TFT panels having a large size (one side of 2 m or more).

Abstract

La présente invention a pour objet une plaque de verre pour substrat, qui contient peu de B2O3 et possède une valeur de β-OH (mm-1) allant de 0,05 à 0,5. La plaque de verre pour substrat est appropriée à une utilisation en tant que plaque de verre pour panneau TFT. La présente invention concerne spécifiquement une plaque de verre pour substrat, qui possède une composition de matrice vitreuse comprenant, en % en moles sur la base des oxydes, de 67 à 72 de SiO2, de 1 à 7 de Al2O3, de 0 à 4 de B2O3, de 11 à 15 de MgO, de 0 à 3 de CaO, de 0 à 3 de SrO, de 0 à 4 de BaO, de 0 à 4 de ZrO2, de 8 à 15 de Na2O et de 0 à 7 de K2O, SiO2 + Al2O3 allant de 71 à 77, MgO + CaO + SrO + BaO allant de 11 à 17 et Na2O + K2O allant 8 à 17, ladite composition de matrice vitreuse satisfaisant à : K2O / (Na2O + K2O) ≤ 0,13 × (SiO2 + Al2O3 + 0,5 B2O3 + 0,3 BaO) - 9,4. La plaque de verre pour substrat possède une valeur de β-OH (mm-1) allant de 0,05 à 0,5 et un rapport de retrait thermique (C) pas supérieur à 16 ppm.
PCT/JP2010/068410 2009-10-19 2010-10-19 Plaque de verre pour substrat, son procédé de production, et procédé de production d'un panneau tft WO2011049100A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201080043823.2A CN102574725B (zh) 2009-10-19 2010-10-19 基板用玻璃板、其制造方法及tft面板的制造方法
EP10824949.1A EP2492246A4 (fr) 2009-10-19 2010-10-19 Plaque de verre pour substrat, son procédé de production, et procédé de production d'un panneau tft
JP2011537269A JP5761025B2 (ja) 2009-10-19 2010-10-19 基板用ガラス板、その製造方法およびｔｆｔパネルの製造方法
US13/435,222 US8791036B2 (en) 2009-10-19 2012-03-30 Glass plate for substrate, method for producing same, and method for producing TFT panel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-240204 2009-10-19
JP2009240204 2009-10-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/435,222 Continuation US8791036B2 (en) 2009-10-19 2012-03-30 Glass plate for substrate, method for producing same, and method for producing TFT panel

Publications (1)

Publication Number Publication Date
WO2011049100A1 true WO2011049100A1 (fr) 2011-04-28

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PCT/JP2010/068410 WO2011049100A1 (fr) 2009-10-19 2010-10-19 Plaque de verre pour substrat, son procédé de production, et procédé de production d'un panneau tft

Country Status (7)

Country Link
US (1) US8791036B2 (fr)
EP (2) EP2805929A1 (fr)
JP (1) JP5761025B2 (fr)
KR (1) KR20120098601A (fr)
CN (1) CN102574725B (fr)
TW (1) TWI461381B (fr)
WO (1) WO2011049100A1 (fr)

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WO2012101221A1 (fr) * 2011-01-28 2012-08-02 Kornerstone Materials Technology Co., Ltd Verre d'aluminosilicate alcalin hautement résistant
US20120208309A1 (en) * 2009-10-19 2012-08-16 Asahi Glass Company, Limited Glass plate for substrate, method for producing same, and method for producing tft panel
US20120234368A1 (en) * 2011-03-09 2012-09-20 Saint-Gobain Glass France Substrate for photovoltaic cell
WO2013136949A1 (fr) * 2012-03-14 2013-09-19 旭硝子株式会社 Plaque de verre flotté et son procédé de fabrication
EP2426093A4 (fr) * 2009-04-28 2014-05-14 Asahi Glass Co Ltd Plaque de verre pour substrat
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JP6601493B2 (ja) * 2015-05-28 2019-11-06 Ａｇｃ株式会社 ガラス基板、および積層基板
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TW201118053A (en) 2011-06-01
CN102574725A (zh) 2012-07-11
CN102574725B (zh) 2014-12-17
JPWO2011049100A1 (ja) 2013-03-14
EP2805929A1 (fr) 2014-11-26
US8791036B2 (en) 2014-07-29
KR20120098601A (ko) 2012-09-05
EP2492246A4 (fr) 2014-06-11

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